Dyeing composition for dyeing keratinous fibres comprising a cationic azo-dye

ABSTRACT

The invention concerns a novel dyeing composition for dyeing keratinous fibres, in particular human hair, comprising a cationic azo-dye of formula (I): W1-N═N—W2-W3, as well as the dyeing method using said composition and the novel compounds of formula (I).

[0001] A subject matter of the invention is a novel dyeing composition for the dyeing of keratinous fibers, in particular of human hair, comprising a specific cationic azo dye and the process for dyeing keratinous fibers employing such a composition. Another subject matter of the invention is novel cationic azo dyes.

[0002] It is known to dye keratinous fibers and in particular human hair with dyeing compositions comprising oxidation dye precursors, generally known as oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, in combination with oxidizing substances, give rise to colored compounds by an oxidative coupling process.

[0003] It is also known that the hues obtained with these oxidation bases can be varied by combining them with couplers or coloring modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols meta-diphenols and certain heterocyclic compounds, such as indole compounds.

[0004] The variety of the molecules employed as oxidation bases and couplers makes it possible to obtain a rich palette of colors.

[0005] This oxidation dyeing process consists in applying, to the keratinous fibers, oxidation bases or a mixture of oxidation bases and of couplers with an oxidizing agent, for example aqueous hydrogen peroxide solution, in leaving to stand and in then rinsing the fibers. The colorations which result therefrom are permanent and powerful, and withstand external agents, in particular light, bad weather, washing, perspiration and rubbing. Generally applied at basic pH, they make it possible to obtain dyeing and simultaneously lightening of the fiber, which is reflected in practice by the possibility of obtaining a final coloration which is lighter than the original color. In addition, lightening the fiber has the advantageous effect of producing a unified color in the case of gray hair and, in the case of naturally pigmented hair, of making the color emerge, that is to say of rendering it more visible.

[0006] It is also known to dye human keratinous fibers by direct dyeing. The process conventionally used in direct dyeing consists in applying, to the keratinous fibers, direct dyes, which are colored and coloring molecules having an affinity for the fibers, in leaving to stand and in then rinsing the fibers.

[0007] It is known, for example, to use nitrobenzene, anthraquinone or nitropyridine direct dyes, azo, xanthene, acridine or azine dyes or triarylmethane dyes.

[0008] The colorations which result therefrom are particularly chromatic colorations which, however, are temporary or semipermanent because the nature of the interactions which bind the direct dyes to the keratinous fiber and their desorption from the surface and/or from the core of the fiber are responsible for their low dyeing power and for their poor resistance to washing or to perspiration. In addition, these direct dyes are generally sensitive to light, because of the low resistance of the chromophore with regard to photochemical attacks, and result over time in fading of the coloring of the hair. In addition, their sensitivity to light is dependent on their distribution, uniform or nonuniform, in the keratinous fiber.

[0009] It is known to use direct dyes in combination with oxidizing agents. However, direct dyes are generally sensitive to the action of oxidizing agents, such as aqueous hydrogen peroxide solution, and reducing agents, such as sodium bisulfite, which generally renders them difficult to use in compositions for lightening direct dyeing based on aqueous hydrogen peroxide solution and based on a basifying agent or in oxidation dyeing compositions in combination with oxidation dye precursors or couplers.

[0010] For example, provision has been made, in Patent Applications FR-1 584 965 and JP-062 711 435, to dye the hair with dyeing compositions based on direct nitro dyes and/or on disperse azo dyes and on aqueous ammoniacal hydrogen peroxide solution by applying, to the hair, a mixture of said dyes and of said oxidizing agent prepared immediately before use. However, the colorations obtained prove to be insufficiently persistent and disappear on shampooing, allowing the lightening of the hair fiber to become apparent. Such a coloration becomes unattractive on changing over time.

[0011] Provision has also been made, in Patent Applications JP-53 95693 and JP 55 022638, to dye the hair with compositions based on cationic direct dyes of oxazine type and on aqueous ammoniacal hydrogen peroxide solution by applying, to the hair, in a first stage, aqueous ammoniacal hydrogen peroxide solution and then, in a second stage, a composition based on the direct oxazine dye. This coloration is not satisfactory because of the fact that it requires a process rendered excessively slow by the leave-in times of the two successive stages. Furthermore, if a mixture prepared at the time of use of the direct oxazine dye with aqueous ammoniacal hydrogen peroxide solution is applied to the hair, no coloration is produced or, at least, a coloration of the hair fiber is obtained which is virtually nonexistent.

[0012] More recently, Patent Application FR 2 741 798 has disclosed dyeing compositions comprising direct azo or azomethine dyes comprising at least one quaternized nitrogen atom, said compositions having to be mixed at the time of use at basic pH with an oxidizing composition. These compositions make it possible to obtain colorations with homogeneous, persistent and bright highlights. However, they do not make it possible to dye keratinous fibers with as much power as with oxidation dyeing compositions.

[0013] There thus exists a real need to try to find chromatic direct dyes which make it possible to dye keratinous fibers as powerfully as oxidation dyes, which are as stable as them toward light and are also resistant to bad weather, washing and perspiration, and which, in addition, are sufficiently stable in the presence of oxidizing and reducing agents to be able to simultaneously obtain lightening of the fiber, either by use of lightening direct compositions comprising them or by the use of oxidation dyeing compositions comprising them. There also exists a real need to try to find direct dyes which make it possible to dye keratinous fibers in order to obtain a very broad range of colors, in particular highly chromatic colors, without forgetting the “basic” shades, such as the blacks and the browns.

[0014] These aims are achieved with the present invention, a subject matter of which is a composition for dyeing keratinous fibers, and in particular human keratinous fibers such as the hair, comprising at least one cationic azo dye of the following formula (I):

W₁—N═N—W₂—W₃

[0015] in which

[0016] W₁ represents a 5-membered cationic aromatic heterocycle of the following formula (II)

[0017] W₂ represents a divalent carbonaceous aromatic or pyridine group of the following formulae (III) or (IV)

[0018] W₃ represents a 5- or 6-membered heterocycle of the following formula (V)

[0019] in which formulae

[0020] Z₁ represents an oxygen or sulfur atom or a radical NR₁₂,

[0021] Z₂ represents a nitrogen atom or a radical CR₁₁,

[0022] R₉ and R₁₂ represent, independently of one another, a C₁-C₈ alkyl radical, optionally substituted by one or more radicals chosen from a hydroxyl, a C₁-C₂ alkoxy, a C₂-C₄ (poly)hydroxyalkoxy radical, an amino, a C₁-C₂ (di)alkylamino, a carboxyl, a sulfonic; an optionally substituted phenyl radical,

[0023] R₁₀ and R₁₁ represent, independently of one another, a hydrogen atom; a C₁-C₄ alkyl radical, optionally substituted by one or more radicals chosen from a hydroxyl, a C₁-C₂ alkoxy, a C₂-C₄ (poly)hydroxyalkoxy radical, an amino, a C₁-C₂ (di)alkylamino, a carboxyl, a sulfonic; an optionally substituted phenyl radical; a carboxyl radical; a sulfonylamino radical;

[0024] R₅, R₆, R₇ and R₈ represent, independently of one another, a hydrogen atom; a chlorine atom; a bromine atom; a linear or branched C₁-C₆ hydrocarbonaceous chain, which can form one or more 3- to 6-membered carbonaceous rings, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbonaceous chain can be replaced by an oxygen, nitrogen or sulfur atom or by an SO₂ group, and the carbon atoms of which can be, independently of one another, substituted by one or more halogen atoms; R₅, R₆, R₇ and R₈ not comprising a peroxide bond, or diazo or nitroso radicals,

[0025] n is an integer equal to 0 or 1,

[0026] R₀, R₁, R₂, R₃ and R₄ represent, independently of one another, a hydrogen atom, a hydroxyl radical; an amino radical; an acetoxy radical; a group —NR₁₃R₁₄, R₁₃ and R₁₄ representing, independently of one another, a hydrogen atom, a C₁-C₄ alkyl radical substituted by one or more radicals chosen from a halogen atom, a hydroxyl, C₁-C₂ alkoxy, amino or C₁-C₂ amino(di)alkyl radical; a sulfonylamino radical; a carboxyl radical; a carboxamido radical; an amido radical; a mono- or dialkylamido radical; a halogen; a C₁-C₆ alkyl radical substituted by one or more radicals chosen from a hydroxyl, C₁-C₂ alkoxy, C₂-C₄ (poly)hydroxyalkoxy, amino, or C₁-C₂ (di)alkylamino radical,

[0027] it being understood that at least one of the groups R₀, R₁, R₂, R₃ and R₄ is different from hydrogen,

[0028] X is an organic or inorganic anion.

[0029] In the context of the present invention, the expression “alkyl”, unless otherwise stated, is understood to mean an alkyl radical comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, which may be linear or branched. The term alkoxy means alkyl-O—, the term alkyl having the above meaning.

[0030] According to the invention, when it is indicated that one or more of the carbon atoms of the hydrocarbonaceous chain defined for the radicals R₅ to R₈ can be replaced by an oxygen, nitrogen or sulfur atom or by an SO₂ group, and/or that these hydrocarbonaceous chains are unsaturated, this means that it is possible, by way of example, to carry out the following conversions:

[0031] In particular, the expression “branched hydrocarbonaceous chain” is understood to mean a chain which can form one or more 3- to 6-membered carbonaceous rings. The expression unsaturated hydrocarbonaceous chain is understood to mean a chain which can have one or more double bonds and/or one or more triple bonds, it being possible for this hydrocarbonaceous chain to give aromatic groups.

[0032] The asymmetric carbons substituted by the radicals R₀, R₁, R₂, R₃ and R₄ can be of the (R) and/or (S) configuration.

[0033] According to the invention, R₀, R₁, R₂, R₃ and R₄ preferably represent a hydroxyl, acetoxy, amino, methylamino, dimethylamino, 2-hydroxyethylamino, carboxyl, carboxamido, amido, mono- or dialkylamido radical.

[0034] According to a particular embodiment, R₀, R₁, R₂, R₃, R₄ and n are chosen from the following combinations: R₀ R₁ R₂ R₃ R₄ n COOH H H H H 0 or 1 COOH OH H H H 0 or 1 CONH2 H H H H 0 or 1 CONH2 OH H H H 0 or 1 CONMe2 H H H H 0 or 1 CONMe2 OH H H H 0 or 1 CH2OH H H H H 0 or 1 CH2OH OH H H H 0 or 1 CH2OH H H CH2OH H 0 H OH H H H 0 or 1 H OH OH H H 0 or 1 H NH2 H H H 0 or 1 H NHMe H H H 0 or 1 H NMe2 H H H 0 or 1 H OH NH2 H H 0 or 1 H OH NHMe H H 0 or 1 H OH NH—CH2—CH—OH H H 0 or 1

[0035] Preferably, R₀, R₁, R₂, R₃ and R₄ are chosen from the following combinations: R₀ R₁ R₂ R₃ R₄ COOH H H H H COOH OH H H H CONMe2 H H H H CH2OH H H H H CH2OH OH H H H H OH H H H H NH2 H H H

[0036] The radicals R₅, R₆, R₇ and R₈ are preferably chosen from a hydrogen atom, a methyl, ethyl, isopropyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl, 1-aminoethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1,2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, 2-hydroxy-1-aminoethyl, methoxy, ethoxy, 3-hydroxyethyloxy, 3-aminoethyloxy, amino, methylamino, dimethylamino and 2-hydroxyethylamino radical. According to a preferred embodiment, R₅, R₆, R₇ and R₈ are chosen from a hydrogen atom, a methyl, hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, methoxy, 2-hydroxyethoxy, amino and 2-hydroxyethylamino radical, more preferably a hydrogen atom, a methyl radical, a methoxy radical and an amino radical.

[0037] According to the invention, R₉ and R₁₂ preferably represent a C₁-C₄ alkyl radical optionally substituted by one or more radicals chosen from a hydroxyl, a C₁-C₂ alkoxy, an amino, a C₁-C₂ (di)alkylamino, a carboxyl, a sulfonic, a phenyl, more preferably a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2-carboxyethyl and 2-sulfonylethyl radical.

[0038] According to the invention, R₁₀ and R₁₁, preferably represent a hydrogen atom, a C₁-C₄ alkyl radical optionally substituted by one or more radicals chosen from a hydroxyl, an amino, a C₁-C₂ (di)alkylamino, a carboxyl, a phenyl, preferably R₁₀ and R₁₁ represent a hydrogen atom, a methyl, ethyl, 2-hydroxyethyl, carboxyl, 1-carboxymethyl, 2-carboxyethyl and 2-sulfonylethyl radical.

[0039] According to the present invention, the composition comprises an azo dye of formula (I) as defined above in which Z1 is —NR₁₂ and W2 is a divalent group of formula (III).

[0040] According to a preferred embodiment, the composition of the present invention comprises an azo dye of formula (I) as defined above in which Z1 is —NR₁₂, W2 is a divalent group of formula (III), Z₂ is CR₁₁.

[0041] The inorganic or organic anion X may be chosen from a halide such as chloride, bromide, fluoride, iodide; a hydroxide; a sulfate; a hydrogen sulfate; a (C₁-C₆)alkyl sulfate such as for example a methyl sulfate or an ethyl sulfate; an acetate; a tartrate; an oxalate; a (C₁-C₆)alkyl sulfonate such as methyl sulfonate; an aryl sulfonate which is unsubstituted or substituted by a C₁-C₄ alkyl radical such as for example a 4-toluoyl sulfonate.

[0042] The concentration of cationic azo dye of formula (I) can vary between 0.001 and 5% by weight approximately relative to the total weight of the dyeing composition, and preferably between approximately 0.05 and 2%.

[0043] The composition of the invention can furthermore comprise an oxidizing agent. This oxidizing agent can be any oxidizing agent conventionally used for bleaching keratinous fibers. The oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates. The use of hydrogen peroxide is particularly preferred.

[0044] The composition according to the invention can furthermore comprise an oxidation base. This oxidation base can be chosen from the oxidation bases conventionally used in oxidation dyeing, for example para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.

[0045] Mention may more particularly be made, among para-phenylenediamines, by way of example, of para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-(β-hydroxyethyl)-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl, β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine, N-(4′-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-(β-hydroxyethyloxy)-para-phenylenediamine, 2-(β-acetylaminoethyloxy)-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 4-(aminophenyl)pyrrolidine, 2-thienyl-para-phenylenediamine, 2-(β-hydroxyethylamino)-5-aminotoluene, and their addition salts with an acid.

[0046] Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-(β-hydroxyethyl)-para-phenylenediamine, 2-(β-hydroxyethyloxy)-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-(β-acetylaminoethyloxy)-para-phenylenediamine, and their addition salts with an acid, are particularly preferred.

[0047] Mention may be made, among bisphenylalkylene-diamines, by way of example, of N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine, N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(4-methylaminophenyl)tetramethylenediamine, N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)-ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and their addition salts with an acid.

[0048] Mention may be made, among para-aminophenols, by way of example, of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-(hydroxymethyl)phenol, 4-amino-2-methylphenol, 4-amino-2-(hydroxymethyl)phenol, 4-amino-2-(methoxymethyl)phenol, 4-amino-(2-aminomethyl)phenol, 4-amino-2-[(β-hydroxy-ethyl)aminomethyl]phenol, 4-amino-2-fluorophenol, and their addition salts with an acid.

[0049] Mention may be made, among ortho-aminophenols, by way of example, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol, and their addition salts with an acid.

[0050] Mention may be made, among heterocyclic bases, by way of example, of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

[0051] Mention may be made, among pyridine derivatives, of the compounds disclosed, for example, in Patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine, and their addition salts with an acid.

[0052] Mention may be made, among pyrimidine derivatives, of the compounds disclosed, for example, in Patents DE 2 359 399, JP 88-169 571, JP 05 163 124 or EP 0 770 375 or Patent Application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine or 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives, such as those mentioned in Patent Application FR-A-2 750 048, among which may be mentioned pyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, pyrazolo[1,5-a]pyrimidine-3,5-diamine, 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine, 3-aminopyrazolo[1,5-a]pyrimidin-7-ol, 3-aminopyrazolo[1,5-a]pyrimidin-5-ol, 2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol, 2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)(2-hydroxyethyl)amino]ethanol, 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 3-amino-5-methyl-7-(imidazolylpropylamino)pyrazolo[1,5-a]pyrimidine, and their addition salts with an acid and their tautomeric forms, when a tautomeric equilibrium exists.

[0053] Mention may be made, among pyrazole derivatives, of the compounds disclosed in Patents DE 3 843 892 and DE 4 133 957 and Patent Applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-(hydroxymethyl)pyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-(methylamino)pyrazole, 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and their addition salts with an acid.

[0054] The composition according to the invention can additionally comprise one or more couplers conventionally used for the conventional oxidation dyeing of keratinous fibers. Mention may in particular be made, among these couplers, of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers and heterocyclic couplers.

[0055] Mention may be made, by way of example, of 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol, 1-(β-hydroxyethylamino)-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(β-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(β-hydroxyethylamino)toluene, and their addition salts with an acid.

[0056] In the composition of the present invention, the coupler or couplers are generally present in an amount of between 0.001 and 10% by weight approximately of the total weight of the dyeing composition and more preferably from 0.005 to 6%. The oxidation base or bases are present in an amount preferably of between 0.001 and 10% by weight approximately of the total weight of the dyeing composition and more preferably from 0.005 to 6%.

[0057] Generally, the addition salts with an acid which can be used in the context of the dyeing compositions of the invention for the oxidation bases and the couplers are chosen in particular from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

[0058] The dyeing composition in accordance with the invention can additionally contain direct dyes different from those of formula (I), it being possible for these dyes in particular to be chosen from nitro dyes of the benzene series, cationic direct dyes, direct azo dyes and direct methine dyes.

[0059] The medium acceptable for dyeing, also referred to as dyeing support, is generally composed of water or of a mixture of water and of at least one organic solvent, in order to dissolve the compounds which would not be sufficiently soluble in water. Mention may be made, as organic solvent, for example, of lower C₁-C₄ alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether; and aromatic alcohols, such as benzyl alcohol or phenoxyethanol; and their mixtures.

[0060] The solvents can be present in proportions preferably of between 1 and 40% by weight approximately with respect to the total weight of the dyeing composition and more preferably still between 5 and 30% by weight approximately.

[0061] The dyeing composition in accordance with the invention can also include various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surface-active agents or their mixtures, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or their mixtures, inorganic or organic thickening agents and in particular anionic, cationic, nonionic and amphoteric associative polymer thickeners, antioxidants, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, conditioning agents, such as, for example, volatile or nonvolatile and modified or unmodified silicones, film-forming agents, ceramides, preservatives or opacifying agents.

[0062] These above adjuvants are generally present in an amount of, for each of them, between 0.01 and 20% by weight with respect to the weight of the composition.

[0063] Of course, a person skilled in the art will take care to choose this or these optional additional compounds so that the advantageous properties intrinsically attached to the dyeing composition in accordance with the invention are not, or not substantially, detrimentally affected by the envisaged addition or additions.

[0064] The pH of the dyeing composition in accordance with the invention is generally between 3 and 12 approximately and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents commonly used in dyeing keratinous fibers or alternatively using conventional buffer systems.

[0065] Mention may be made, among acidifying agents, by way of example, of inorganic or organic acids, such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, such as acetic acid, tartaric acid, citric acid or lactic acid, or sulfonic acids.

[0066] Mention may be made, among basifying agents, by way of example, of ammonia, alkaline carbonates, alkanolamines, such as mono-, di- and triethanolamines, and their derivatives, sodium hydroxide, potassium hydroxide and the compounds of following formula (III):

[0067] in which W is a propylene residue optionally substituted by a hydroxyl group or a C₁-C₄ alkyl radical and R₆, R₇, R₈ and R₉, which are identical or different, represent a hydrogen atom or a C₁-C₄ alkyl or C₁-C₄ hydroxyalkyl radical.

[0068] The dyeing composition according to the invention can be provided in various forms, such as in the form of liquids, creams or gels or in any other form appropriate for carrying out dyeing of keratinous fibers and in particular of human hair.

[0069] Another subject matter of the invention is a direct dyeing process which comprises the application of a dyeing composition comprising a dye of formula (I) as defined above to keratinous fibers. After a leave-in time, the keratinous fibers are rinsed, allowing colored fibers to appear.

[0070] The application to the fibers of the dyeing composition comprising the cationic azo dye of formula (I) can be carried out in the presence of an oxidizing agent which brings about the bleaching of the fiber. This oxidizing agent can be added to the composition comprising the cationic azo dye at the time of use or directly to the keratinous fiber. According to a specific embodiment, the composition comprising the cationic azo dye of formula (I) is free of oxidation base and of coupler.

[0071] Another subject matter of the invention is an oxidation dyeing process which comprises the application to fibers of a dyeing composition which comprises a dye of formula (I), at least one oxidation base and optionally at least one coupler, in the presence of an oxidizing agent.

[0072] The oxidation base, the coupler and the oxidizing agent are as defined above.

[0073] In the context of permanent oxidation dyeing, it is also possible to use, as oxidizing agent, enzymes among which may be mentioned peroxidases, 2-electron oxidoreductases, such as uricases, and 4-electron oxygenases, such as laccases.

[0074] The color can be developed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention either at the time of use or it can be employed from an oxidizing composition comprising it, applied to the fibers simultaneously with or sequentially to the dyeing composition.

[0075] In the case of permanent oxidation dyeing or of direct dyeing, the dyeing composition is mixed, preferably at the time of use, with a composition comprising, in a medium acceptable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to develop a coloring. The mixture obtained is subsequently applied to the keratinous fibers. After a leave-in time of 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, the keratinous fibers are rinsed, washed with a shampoo, rinsed again and then dried.

[0076] The oxidizing composition can also include various adjuvants conventionally used in hair dyeing compositions and as defined above.

[0077] The pH of the oxidizing composition including the oxidizing agent is such that, after mixing with the dyeing composition, the pH of the resulting composition applied to keratinous fibers preferably varies between 3 and 12 approximately, and more preferably still between 5 and 11. It can be adjusted to the desired value by means of acidifying or basifying agents commonly used in dyeing keratinous fibers and as defined above.

[0078] The composition which is finally applied to the keratinous fibers can be provided in various forms, such as in the form of liquids, creams or gels or in any other form appropriate for carrying out dyeing of keratinous fibers and in particular of human hair.

[0079] Another subject matter of the invention is a multi-compartment device or dyeing ‘kit’ in which a first compartment includes the dyeing composition of the invention and a second compartment includes the oxidizing composition. This device can be equipped with a means allowing the desired mixture to be delivered to the hair, such as the devices disclosed in Patent FR 2 586 913 on behalf of the Applicant Company.

[0080] Finally, another subject matter of the invention is the cationic azo dyes of formula (I) as defined above. These compounds can be obtained from the preparation processes described for example in the documents EP 810824, GB 9619573, RO 106572, J. Chem. Res., Synop. (1998), (10), 648-649, DE 19721619, U.S. Pat. No. 5,852,179, Synth. Commun 1999, 29(13), 2271-2276.

[0081] The following examples serve to illustrate the invention without, however, exhibiting a limiting nature.

EXAMPLES OF SYNTHESIS Example No. 1

[0082] Preparation of a Compound of Formula:

[0083] 2-[4-(3-Hydroxypyrrolidine-1-yl)phenylazo)-1,3-dimethyl-3H-imidazol-1-ium perchlorate.

[0084] 2.5 g (7.6 mmol) of 2-(4-methoxyphenylazo)-1,3-dimethyl-3H-imidazol-1-ium perchlorate and 50 ml of 2-propanol are charged to a fully equipped round-bottomed flask. The mixture is brought to 60° C. 1.3 g (15.2 mmol) of pyrrolidine are added. This mixture is brought, with stirring, to the reflux temperature of the solvent for 3 hours.

[0085] With stirring, the reaction mixture is allowed to return to ambient temperature and a red solid is isolated by filtration; the latter is washed 3 times with diisopropyl ether.

[0086] After drying under vacuum at 30° C., 2.6 g of 2-[4-(3-hydroxypyrrolidine-1-yl)phenylazo)-1,3-dimethyl-3H-imidazol-1-ium perchlorate are recovered in the form of a red powder.

[0087] The characteristics of this product are as follows:

[0088] Mass ESI+: m/z=327[M⁺] ¹H NMR: (400 MHz-DMSO) ppm: 1.88 (m-1H); 2.27 (m-1H); 3.18 (m-1H); 3.72 (m-2H); 4.25 (m-1H) pyrrolidine 3.91 (s-6H) —NCH₃; 6.61 (d-2H); 7.75 (d-2H) phenyl 7.47 (s-2H) imidazole

[0089] A dye giving a Bordeaux red color is thus obtained.

Example No. 2

[0090] Preparation of a Compound of Formula:

[0091] 2-[4-(3-Acetamidopyrrolidine-1-yl)phenylazo)-1,3-dimethyl-3H-imidazol-1-ium perchlorate.

[0092] 1.25 g (3.8 mmol) of 2-(4-methoxyphenylazo)-1,3-dimethyl-3H-imidazol-1-ium perchlorate and 15 ml of 2-propanol are charged to a fully equipped reactor. The mixture is brought to 60° C. 0.96 g (7.6 mmol) of acetamidopyrrolidine is added. This mixture is brought, with stirring, to the reflux temperature of the solvent for 3 hours.

[0093] With stirring, the reaction mixture is allowed to return to ambient temperature and the red solid is isolated by filtration. The latter is washed 3 times with diisopropyl ether.

[0094] After drying under vacuum at 30° C. to a constant weight, 0.5 g of 2-[4-(3-acetamidopyrrolidine-1-yl)phenylazo)-1,3-dimethyl-3H-imidazol-1-ium perchlorate is recovered.

[0095] Analyses: Mass ESI+: m/z=327[M⁺] ¹H NMR: (400 MHz-CD3OD) ppm: 2.1 (s-3H); 2.12 (m-1H); 3.18 (m-1H); 2.34 (m-1H); 3.47 (m-1H) pyrrolidine 3.95 (s-6H) —NCH₃; 6.78 (d-2H); 7.96 (d-2H) phenyl 7.39 (s-2H) imidazole

[0096] A dye giving a red color is thus obtained.

Example No. 3

[0097] Preparation of a Compound of Formula:

[0098] 2-[4-(4-Hydroxypiperidin-1-yl)phenylazo]-1,3-dimethyl-3H-imidazol-1-ium perchlorate

[0099] Using the same procedure as that of example 2, the above compound is obtained.

[0100] Analyses: Mass ESI+: m/z=300[M⁺] ¹H NMR: (400 MHz-CD30D ppm: 1.27 (m-2H); 1.66 (m-2H); 3.19 (m-2H); 3.74 (m-1H); 4.66 (m-1H); 4.16 (m-1H) piperidine 3.74 (s-6H) —NCH₃; 6.95 (d-2H); 7.80 (d-2H) phenyl 7.49 (s-2H) imidazole

[0101] A dye giving a dark purple-red color is thus obtained.

Dyeing Examples

[0102] The following dyeing compositions were prepared: Quantity per 100 g of composition Cetylstearyl alcohol (C16/C18 50/50) 19.21 Oleyl alcohol 3.20 Oxyethylenated oleocetyl alcohol 4.27 Perfume 0.59 Diethylenetriaminepentaacetic acid, 2.37 pentasodium salt (40%) Monoethanolamine 0.75 Oleic acid 3.20 Tetramethylhexamethylenediamine/1,3-di- 5.93 chloropropylene polycondensate Aqueous ammonia (40%) 13.00 Dye 1.25 Distilled water qs 100

[0103] The composition is mixed with the 20-volumes cream oxidizing agent (1/1.5 m/m) so that the final dye concentration is 0.5%. The mixture is applied to locks of hair comprising natural and permanently waved 90% white hair. 10 g of composition are applied per 1 g of lock. After allowing the mixture to act for 35 minutes at ambient temperature, the locks are rinsed, shampooed, rinsed again and dried.

[0104] Each lock is evaluated before and after dyeing in the L*a*b* system, by means of a CM 2002 MINOLTA® spectrophotometer (illuminant D65).

[0105] In the L*a*b* space, the lightness is indicated by the value L* on a scale from 0 to 100 whereas the chromatic coordinates are expressed by a* and b* which indicate two color axes, a* the red-green axis and b* the yellow-blue axis.

[0106] According to this system, the higher the value of L, the lighter and less intense the color. Conversely, the lower the value of L, the darker or more intense the color.

[0107] The following dyeing results were obtained. Natural hair Permanently waved hair L* a* b* L* a* b* Dye of 28.71 41.19 5.57 25.53 35.21  9.58 example 1 Dye of 33.79 42.05 4.27 27.72 37.81 10.06 example 2 Dye of 25.51 33.59 8.25 23.37 29.45 10.24 example 3 

1. A composition for dyeing keratinous fibers, and in particular human keratinous fibers such as the hair, comprising at least one cationic azo dye of the following formula (I): W₁—N═N—W₂—W₃ in which W₁ represents a 5-membered cationic aromatic heterocycle of the following formula (II)

W₂ represents a divalent aromatic carbonaceous or pyridine group of the following formulae (III) or (IV)

W₃ represents a 5- or 6-membered heterocycle of the following formula (V)

in which formulae Z₁ represents an oxygen or sulfur atom or a radical NR₁₂, Z₂ represents a nitrogen atom or a radical CR₁₁, R₉ and R₁₂ represent, independently of one another, a C₁-C₈ alkyl radical, optionally substituted by one or more radicals chosen from a hydroxyl, a C₁-C₂ alkoxy, a C₂-C₄ (poly)hydroxyalkoxy radical, an amino, a C₁-C₂ (di)alkylamino, a carboxyl, a sulfonic; an optionally substituted phenyl radical, R₁₀ and R₁₁ represent, independently of one another, a hydrogen atom; a C₁-C₄ alkyl radical, optionally substituted by one or more radicals chosen from a hydroxyl, a C₁-C₂ alkoxy, a C₂-C₄ (poly)hydroxyalkoxy radical, an amino, a C₁-C₂ (di)alkylamino, a carboxyl, a sulfonic; an optionally substituted phenyl radical; a carboxyl radical; a sulfonylamino radical; R₅, R₆, R₇ and R₈ represent, independently of one another, a hydrogen atom; a chlorine atom; a bromine atom; a linear or branched C₁-C₆ hydrocarbonaceous chain, which can form one or more 3- to 6-membered carbonaceous rings, and which can be saturated or unsaturated, of which one or more carbon atoms of the carbonaceous chain can be replaced by an oxygen, nitrogen or sulfur atom or by an SO₂ group, and the carbon atoms of which can be, independently of one another, substituted by one or more halogen atoms; R₅, R₆, R₇ and R₈ not comprising a peroxide bond, or diazo or nitroso radicals, n is an integer equal to 0 or 1, R₀, R₁, R₂, R₃ and R₄ represent, independently of one another, a hydrogen atom, a hydroxyl radical; an amino radical; an acetoxy radical; a group —NR₁₃R₁₄, R₁₃ and R₁₄ representing, independently of one another, a hydrogen atom, a C₁-C₄ alkyl radical substituted by one or more radicals chosen from a halogen atom, a hydroxyl, C₁-C₂ alkoxy, amino or C₁-C₂ amino(di)alkyl radical; a sulfonylamino radical; a carboxyl radical; a carboxamido radical; an amido radical; a mono- or dialkylamido radical; a halogen; a C₁-C₆ alkyl radical substituted by one or more radicals chosen from a hydroxyl, C₁-C₂ alkoxy, C₂-C₄ (poly)hydroxyalkoxy, amino, or C₁-C₂ (di)alkylamino radical, it being understood that at least one of the groups R₀, R₁, R₂, R₃ and R₄ is different from hydrogen, X is an organic or inorganic anion.
 2. The composition as claimed in claim 1, in which R₀, R₁, R₂, R₃ and R₄ represent, independently of one another, a hydroxyl, acetoxy, amino, methylamino, dimethylamino, 2-hydroxyethylamino, carboxyl, carboxamido, amido, mono- or dialkylamido radical.
 3. The composition as claimed in claim 1 or 2, in which R₀, R₁, R₂, R₃, R₄ and n are chosen from the following combinations: R₀ R₁ R₂ R₃ R₄ n COOH H H H H 0 or 1 COOH OH H H H 0 or 1 CONH2 H H H H 0 or 1 CONH2 OH H H H 0 or 1 CONMe2 H H H H 0 or 1 CONMe2 OH H H H 0 or 1 CH2OH H H H H 0 or 1 CH2OH OH H H H 0 or 1 CH2OH H H CH2OH H 0 H OH H H H 0 or 1 H OH OH H H 0 or 1 H NH2 H H H 0 or 1 H NHMe H H H 0 or 1 H NMe2 H H H 0 or 1 H OH NH2 H H 0 or 1 H OH NHMe H H 0 or 1 H OH NH—CH2—CH—OH H H 0 or 1


4. The composition as claimed in claim 3, in which R₀, R₁, R₂, R₃ and R₄ are chosen from the following combinations: R₀ R₁ R₂ R₃ R₄ COOH H H H H COOH OH H H H CONMe2 H H H H CH2OH H H H H CH2OH OH H H H H OH H H H H NH2 H H H


5. The composition as claimed in any one of claims 1 to 4, in which R₅, R₆, R₇ and R₈ are chosen from a hydrogen atom, a methyl, ethyl, isopropyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl, 1-aminoethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1,2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, 2-hydroxy-1-aminoethyl, methoxy, ethoxy, 3-hydroxyethyloxy, 3-aminoethyloxy, amino, methylamino, dimethylamino and 2-hydroxyethylamino radical.
 6. The composition as claimed in claim 5, in which R₅, R₆, R₇ and R₈ are chosen from a hydrogen atom, a methyl, hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, methoxy and 2-hydroxyethoxy radical, preferably a hydrogen atom, a methyl radical, a methoxy radical, an amino radical.
 7. The composition as claimed in any one of claims 1 to 6, in which R₉ R₁₂ represent, independently of one another, a C₁-C₄ alkyl radical optionally substituted by one or more radicals chosen from a hydroxyl, a C₁-C₂ alkoxy, an amino, a C₁-C₂ (di)alkylamino, a carboxyl, a sulfonic, a phenyl, preferably a methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2-carboxyethyl and 1-sulfonylethyl radical.
 8. The composition as claimed in any one of the preceding claims, in which R₁₀ and R₁₁ represent a hydrogen atom, a C₁-C₄ alkyl radical optionally substituted by one or more radicals chosen from a hydroxyl, an amino, a C₁-C₂ (di)alkylamino, a carboxyl, a phenyl, preferably a hydrogen atom, a methyl, ethyl, 2-hydroxyethyl, carboxyl, 1-carboxymethyl, 2-carboxyethyl and 2-sulfonylethyl radical.
 9. The composition as claimed in any one of the preceding claims, in which Z1 is —NR₁₂, W2 is a divalent group of formula (III).
 10. The composition as claimed in claim 9, in which Z₂ is CR₁₁.
 11. The composition as claimed in any one of claims 1 to 10, furthermore comprising an oxidation base.
 12. The composition as claimed in claim 11, in which the oxidation base is chosen from para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts with an acid.
 13. The composition as claimed in either of claims 11 and 12, in which the oxidation base(s) are present in a quantity between 0.001 and 10%, preferably between 0.005 and 6%.
 14. The composition as claimed in any one of claims 1 to 13, comprising at least one coupler.
 15. The composition as claimed in claim 14, in which the coupler is chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers and heterocyclic couplers and their addition salts with an acid.
 16. The composition as claimed in any one of claims 1 to 15, furthermore comprising an oxidizing agent, preferably hydrogen peroxide.
 17. A process for the oxidation dyeing of keratinous fibers and in particular of human keratinous fibers such as the hair, characterized in that at least one dyeing composition as defined in any one of claims 1 to 10 is applied to the fibers.
 18. The process as claimed in claim 17, in which the dyeing composition contains an oxidizing agent.
 19. The process as claimed in claim 18, in which the oxidizing agent is mixed at the time of use with the dyeing composition.
 20. The process as claimed in either of claims 17 and 18, in which the oxidizing agent is applied to the fibers in the form of an oxidizing composition simultaneously with or sequentially to the dyeing composition.
 21. A process for the oxidation dyeing of the keratinous fibers and in particular of human keratinous fibers such as the hair, characterized in that at least one dyeing composition as defined in any one of claims 1 to 10, furthermore comprising at least one oxidation base and optionally at least one coupler, in the presence of an oxidizing agent, is applied to the fibers.
 22. The process as claimed in claim 21, in which the oxidizing agent is mixed at the time of use with the dyeing process.
 23. The process as claimed in claim 21, in which the oxidizing agent is applied to the fibers in the form of a dyeing composition simultaneously with or sequentially to the dyeing composition.
 24. A multi-compartment device or multi-compartment dyeing “kit”, in which a first compartment comprises a composition as defined in any one of claims 1 to 15 and a second compartment comprises an oxidizing composition.
 25. A cationic azo compound of formula (I) as defined according to any one of claims 1 to
 10. 